CN102321277A - Ionic crosslinked chitosan organic acid salt and anionized chitosan electrolyte composite film and preparation method thereof - Google Patents
Ionic crosslinked chitosan organic acid salt and anionized chitosan electrolyte composite film and preparation method thereof Download PDFInfo
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- CN102321277A CN102321277A CN201110195338A CN201110195338A CN102321277A CN 102321277 A CN102321277 A CN 102321277A CN 201110195338 A CN201110195338 A CN 201110195338A CN 201110195338 A CN201110195338 A CN 201110195338A CN 102321277 A CN102321277 A CN 102321277A
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Abstract
The invention discloses an ionic crosslinked chitosan organic acid salt and anionized chitosan electrolyte composite film, which is prepared from the following materials of chitosan organic acid salt, anionized chitosan, calcium chloride or zinc chloride according to the mass proportion of 1/0.1 to 0.9/0.02 to 0.1. The composite film has better mechanical performance, moisturizing efficiency and unique bacteriostasis and belongs to a biodegradable composite material with the great development potential. The composite film has the advantages that the biocompatibility is good, the degradation performance is controllable, and the like, and can be used as food fresh keeping, biology sterilization and antibacterial materials. Therefore, the composite film can be widely used in the fields of food, medicine, agriculture, daily use articles and the like.
Description
Technical field
The invention belongs to the functional polymer chemical field; Also belong to the natural polymer field; Be specifically related to ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film, it is one type of functional materials with good mechanical performance, biological degradability and antibiotic and sterilizing ability.
Background technology
Chitosan is natural alkaline polysaccharide, contains-NH
2,-OH functional group is prone to modification, forms various verivates, and chitosan and verivate thereof have following characteristic: the good biocompatibility of (1) chitosan, and can be by biological degradation, degraded product is nontoxic; (2) chitosan and verivate thereof have the character of many uniquenesses, like bacterinertness, microbial resistance, the healing etc. of chelating property, antiviral property, anti-carcinogenic property and promotion wound to heavy metal ion.Therefore, can be widely used in fields such as medical science, pharmacy, papermaking, fabric, functional membrane parting material, environmental wastewater processing and biochemistry.
Chitosan has good functional property and potential using value, and one of them noticeable characteristic is exactly a film-forming properties.In recent years, chitosan more and more receives people's attention as a kind of good membranes material.Coating-film fresh-keeping demonstrates wide prospect in foodstuffs industry.In foodstuffs industry, the anti-microbial effect of chitosan receives publicity.Chitosan has very strong inhibition ability to bacterium, and intestinal bacteria, streptococcus aureus, Bacillus proteus, Bacillus subtilus, yeast are all had stronger restraint.People such as summer Wenshui carry out antibacterial tests with regard to chitosan to some common bacteriums, mould and yeast in the food.The result shows that chitosan obviously surpasses control group to bacterium and its bacteriostasis rate of yeast, and along with its bacteriostasis rate of increase of mass concentration becomes big gradually.Chitosan is different to the inhibiting susceptibility of different bacterium, and bacterium is prone to be suppressed, yeast secondly, then restraining effect is smaller to mould, this maybe be relevant with the antibiotic mechanism of chitin oligosaccharide.But, along with the increase of chitin oligosaccharide mass concentration, to all corresponding enhancing of bacteriostatic action of various bacterium.Human hydrolyzing chitosans (molecular weight is 10,000～50,000) such as paddy Tian Xiaoxiong are made antibacterial tests, and the result shows has restraining effect to harmful bacterium, to confirming the quality guaranteed period of food, plays a key effect.People such as Zhang Wei have synthesized water soluble derivatives of chitosan, truly have stronger bacteriostatic action through measuring this material of proof, and its anti-microbial effect are stable to high temperature, high pressure.
Chitosan is coated onto fruit and vegetable surfaces, forms a skim at fruit and vegetable surfaces, and this film has semipermeability, to O
2, CO
2, C
2H
4Have certain selection osmosis, and certain water-retentivity will be arranged.Thereby, stop on the one hand in the extraneous air admission rete, suppress the respiration of fruit and vegetable materials, the carbonic acid gas that breathing is produced escapes, and prevents anaerobic fermentation.The fresh-keeping mechanism of fruits and vegetables tunicle is to regulate intravital oxygen and gas concentration lwevel through the film of fruit and vegetable surfaces, and its respiration is weakened, and reaches fresh-keeping purpose.Simultaneously, the film-forming properties of chitosan has also hindered pathogenic bacteria and has contacted with the direct of host tissue or cell, has reduced effective intrusion of pathogenic bacteria.The thickness of chitosan rete is the principal element that influences fresh-keeping effect.
Humans such as Liu Qingmei 1.5% chitosan+0.5% Sodium Benzoate applies the winter bamboo shoot of tin foil packing; Under the room temperature about 7 ℃ freshness-retained 30 days; The yellowish pink pool of bamboo shoot shell bamboo shoot is constant basically, and good bamboo shoot rate reaches 85%, is superior to other preservation agent sucrose fatty ester, sodium-alginate processing.Using concentration is that 2% chitosan carries out coating-film fresh-keeping to tomato, and preservation is after 15 days, and total acidity total reducing sugar amount, the Vitamin C content of tomato are all approaching with former tomato, and the preservation effect is better than 0.2% Sodium Benzoate solution.People such as Chen Xin are the feedstock production glucosamine hydrochloride with the chitin, and this salt has fresh-keeping effect preferably as the tomato preservation agent.With the mixing solutions coating-film fresh-keeping lichee that contains VC 0.01kg/L and chitosan 0.01kg/L, with comparing of not filming, fruit colour is good, the decayed fruit rate is low, mass loss is little, respiration rate is low.(33～34 ℃) lichee shelf-life can prolong 3d under the room temperature.Cook preservation agent at pears surfaces coated last layer chitosan film, fresh-keeping effect is better than 0 ℃ of cold storing and fresh-keeping effect, can obviously prolong the commodity price phase.Carboxymethylation chitosan water soluble is a kind of good preservation agent, and fruits and vegetables are had certain preservativity.With it cucumber is carried out fresh-keeping, after 12 days its vitamins C, acid, sugar not high by 62% than blank cucumber, 32% and 70%.Chinese honey coating-film fresh-keeping after 23 days its vitamins C, moisture a spot of variation is only arranged, preserved the color, smell and taste of Chinese honey preferably.Apple is freshness-retained more than 9 months, and tomato is more than freshness-retained half a year.
But simple chitosan is used for existing when fresh-keeping that fresh-keeping layer is unstable, shortcoming such as be prone to come off.
Summary of the invention
The objective of the invention is to be dissolved in behind the organic acid and negatively charged ion chitosan blend system film through chitosan; It is crosslinked with divalent calcium or zine ion to handle continued with basic soln, obtains stable ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film.Because of Zn
2+Be than being easier to and one of chitosan chelated metal ion, chitosan-Zn mixture not only keeps even has strengthened the activity of chitosan, has kept Zn simultaneously
2+To the restraining effect of some mikrobes, has the bacteriostatic action of wide spectrum.
The present invention takes following technical scheme: ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film; It is processed by following material: chitosan organic acid salt, anionization chitosan, calcium chloride or zinc chloride, three's mass ratio are 1: 0.1～0.9: 0.02～0.1.
Preferably, the mass concentration of chitosan organic acid salt is 5-95%, and the mass concentration of anionization chitosan is 5-95%, and the mass concentration of calcium chloride or zinc chloride is 1-30%.
Preferably, the chitosan organic acid salt is chitosan ascorbate salt, chitosan malate, chitosan lactate, Chitosan citrate, chitosan bran hydrochlorate, chitosan maleic acid salt, chitosan fumarate, chitosan acetate, chitosan formate or chitosan tartrate; Described anionization chitosan is carboxymethylation chitosan, sulfation chitosan or sulfation CMS.
Composite package of the present invention has mechanical property and rate and the unique biocidal property of preserving moisture preferably, is a kind of biodegradable matrix material with the potentiality that develop on a large scale very much.It has advantages such as good biocompatibility, degradation property be controlled, can be used as food fresh keeping, biological antibiotic and anti-biotic material.Therefore, can be widely used in fields such as food, medical science, agricultural, daily necessities.
The present invention is to be raw material with chitosan and negatively charged ion chitosan, prepares blend film through blend method and handles then and make the electric charge upset obtain the polyelectrolyte composite package, and adopt divalent ion cross-linking modified, and concrete steps are following:
(1) chitosan is dissolved in the organic acid soln of 1%-4% (quality percentage composition), is mixed with the chitosan acylate solution;
(2) the anionization chitosan is dissolved in the Hydrogen chloride of 0.1-2% (quality percentage composition), is mixed with solution;
(3) solution of (1) step with the preparation of (2) step is mixed, curtain coating on sheet glass after drying under the room temperature, is taken off from sheet glass, gets blend film;
(4) blend film is immersed in the ethanolic soln of sodium hydrogencarbonate, yellow soda ash or sodium hydroxide, pH regulator to neutral (7-9), is formed the chitosan derivatives composite package;
(5) adopt saturated calcium chloride or the crosslinked composite package of liquor zinci chloridi, obtain stable ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film.
Preferably, the solvent of dissolving chitosan is an aqueous solutions of organic acids, and organic acid is xitix (being VC), oxysuccinic acid, lactic acid, Hydrocerol A, bran acid, maleic acid, fumaric acid, acetate, formic acid or tartrate.
Preferably, in (3) step, (1) step and the solution in second (2) step are pressed 1: 9-9: 1 (volume ratio) be mixed (W/V).
Preferably, in (3) step, after under the room temperature dry 72 hours, take off, get blend film from sheet glass.
Preferably, in (4) step, blend film is immersed in 75%-95% (quality percentage composition) ethanolic soln of rare sodium hydrogencarbonate, dilute sodium carbonate or dilute sodium hydroxide.
In above-mentioned preparing method's the step, also be technical scheme of the present invention with the exchange of (2) step with (1) step.
The composite package that the present invention makes has good mechanical performance, biological degradability and antibiotic and sterilizing ability, and production process is simple, convenient.Can be used as biodegradable matrix material, food fresh keeping, biological antibiotic and antibiotic and controlled delivery of pharmaceutical agents releasable material, and the water-absorbing material that is used as baby' diaper, sanitary napkin.Therefore, can be widely used in fields such as food, medical science, agricultural, daily necessities.
Description of drawings
Fig. 1 is the synoptic diagram of chitosan malate forming process.
Fig. 2 is the synoptic diagram of zine ion cross-linked chitosan lactic acid salt and CMS pentalyte.
Fig. 3 a, 3b are that calcium ion cross-linked chitosan Citrate trianion and sulfation chitosan electrolyte complex film material are to the strawberry preservation design sketch.
Fig. 4 is zine ion cross-linked chitosan ascorbate salt and the sulfation CMS electrolyte complex film material fungistatic effect figure to subtilis.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1
2.0g chitosan (M
η=80 ten thousand Da) be dissolved in jointly in the deionized water with the 1.5g oxysuccinic acid, form the chitosan malate; With 2g CMS (M
η=14 ten thousand Da) be dissolved in the Hydrogen chloride (0.5%) and be mixed with solution; The two is mixed stirring according to volume ratio at 50%: 50%, leave standstill, deaeration is built it on the sheet glass of 10cm * 10cm, is positioned over 40 ℃ of oven dry down in the baking oven, is prepared into blend film.Blend film is immersed in 95% ethanolic soln of sodium hydroxide,, obtains composite package pH regulator to 7.4.Adopt the saturated calcium chloride solution of 100ml to soak composite package 36 hours, calcium ion cross-linked chitosan malate that must be stable and CMS electrolyte complex film material down in 4 ℃.
Fig. 1 is the synoptic diagram of chitosan malate forming process.
Embodiment 2
1.0g chitosan (M
η=60 ten thousand Da) be dissolved in jointly in the deionized water with 1.0g lactic acid, form chitosan lactate; With 1g CMS (M
η=10 ten thousand Da) be dissolved in the Hydrogen chloride (0.2%) and be mixed with solution; The two is mixed stirring according to volume ratio at 80%: 20%, leave standstill, deaeration is built it on the sheet glass of 8cm * 8cm, is positioned over 50 ℃ of oven dry down in the baking oven, is prepared into blend film.Blend film is immersed in 80% ethanolic soln of sodium hydrogencarbonate,, obtains composite package pH regulator to 7.0.Adopt 5% liquor zinci chloridi of 80ml to soak composite package 24 hours, zine ion cross-linked chitosan lactic acid salt that must be stable and CMS electrolyte complex film material down in 25 ℃.
Fig. 2 is the synoptic diagram of zine ion cross-linked chitosan lactic acid salt and CMS pentalyte.
Embodiment 3
1.8g chitosan (M
η=120 ten thousand Da) be dissolved in jointly in the deionized water with the 1.6g Hydrocerol A, form Chitosan citrate; With 1.2g sulfation chitosan (M
η=8 ten thousand Da) be dissolved in the Hydrogen chloride (1%) and be mixed with solution; The two is mixed stirring according to volume ratio at 90%: 10%, leave standstill, deaeration is built it on the sheet glass of 12cm * 12cm, is positioned over 60 ℃ of oven dry down in the baking oven, is prepared into blend film.Blend film is immersed in 75% ethanolic soln of yellow soda ash,, obtains composite package pH regulator to 8.0.Adopt 20% calcium chloride solution of 90ml to soak composite package 24 hours, calcium ion cross-linked chitosan Citrate trianion that must be stable and sulfation chitosan electrolyte complex film material down in 25 ℃.
Fig. 3 preserves the fresh-keeping effect figure (a be blank, b be composite package fresh-keeping effect) of strawberry after 10 days for it down to room temperature (25 ℃).
Embodiment 4
2.5g chitosan (M
η=70 ten thousand Da) be dissolved in jointly in the deionized water with 1.8g xitix (being VC), form Chitosan citrate; With 1.5g sulfation CMS (M
η=6 ten thousand Da) be dissolved in the Hydrogen chloride (0.4%) and be mixed with solution; The two is mixed stirring according to volume ratio at 85%: 15%, leave standstill, deaeration is built it on the sheet glass of 10cm * 10cm, is positioned over 60 ℃ of oven dry down in the baking oven, is prepared into blend film.Blend film is immersed in 75% ethanolic soln of sodium hydroxide,, obtains composite package pH regulator to 7.0.Adopt 15% liquor zinci chloridi of 75ml to soak composite package 48 hours, zine ion cross-linked chitosan ascorbate salt that must be stable and sulfation CMS electrolyte complex film material down in 25 ℃.
Fig. 4 is zine ion cross-linked chitosan ascorbate salt and the sulfation CMS electrolyte complex film material fungistatic effect figure to subtilis.
Above-mentioned the preferred embodiments of the present invention are specified, those of ordinary skills will be appreciated that the present invention is not limited to the foregoing description, any conversion of the present invention, modification are all fallen into protection scope of the present invention.
Claims (9)
1. ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film; It is characterized in that being processed by following material: chitosan organic acid salt, anionization chitosan, calcium chloride or zinc chloride, three's mass ratio are 1: 0.1～0.9: 0.02～0.1.
2. ionomer chitosan organic acid salt according to claim 1 and anionization chitosan electrolyte complex film; It is characterized in that: the mass concentration of said chitosan organic acid salt is 5-95%; The mass concentration of anionization chitosan is 5-95%, and the mass concentration of calcium chloride or zinc chloride is 1-30%.
3. ionomer chitosan organic acid salt according to claim 1 and 2 and anionization chitosan electrolyte complex film is characterized in that: described chitosan organic acid salt is chitosan ascorbate salt, chitosan malate, chitosan lactate, Chitosan citrate, chitosan bran hydrochlorate, chitosan maleic acid salt, chitosan fumarate, chitosan acetate, chitosan formate or chitosan tartrate; Described anionization chitosan is carboxymethylation chitosan, sulfation chitosan or sulfation CMS.
4. the preparation method of claim 1-3 said ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film is characterized in that as follows:
(1) chitosan is dissolved in the organic acid soln that mass percentage content is 1%-4%, is mixed with the chitosan acylate solution;
(2) the anionization chitosan is dissolved in the Hydrogen chloride that mass percentage content is 0.1-2%, is mixed with solution;
(3) solution of (1) step with the preparation of (2) step is mixed, curtain coating on sheet glass after drying under the room temperature, is taken off from sheet glass, gets blend film;
(4) blend film is immersed in the ethanolic soln of sodium hydrogencarbonate, yellow soda ash or sodium hydroxide, pH regulator to neutral, is formed the chitosan derivatives composite package;
(5) adopt calcium chloride or the crosslinked composite package of liquor zinci chloridi, obtain stable ionomer chitosan organic acid salt and anionization chitosan electrolyte complex film.
5. the preparation method of ionomer chitosan organic acid salt as claimed in claim 4 and anionization chitosan electrolyte complex film; It is characterized in that: the solvent of said dissolving chitosan is an aqueous solutions of organic acids, and organic acid is xitix, oxysuccinic acid, lactic acid, Hydrocerol A, bran acid, maleic acid, fumaric acid, acetate, formic acid or tartrate.
6. the preparation method of ionomer chitosan organic acid salt as claimed in claim 4 and anionization chitosan electrolyte complex film is characterized in that: in (3) step, with the solution by volume 1 of (1) step with second (2) step: 9-9: 1 mixed.
7. like the preparation method of claim 4 or 6 described ionomer chitosan organic acid salts and anionization chitosan electrolyte complex film, it is characterized in that: in (3) step, after under the room temperature dry 72 hours, take off, get blend film from sheet glass.
8. the preparation method of ionomer chitosan organic acid salt as claimed in claim 4 and anionization chitosan electrolyte complex film; It is characterized in that: in (4) step, the mass percentage content that blend film is immersed in sodium hydrogencarbonate, yellow soda ash or sodium hydroxide is in the 75%-95% ethanolic soln.
9. the preparation method of ionomer chitosan organic acid salt as claimed in claim 4 and anionization chitosan electrolyte complex film is characterized in that: (1) step and the exchange of (2) step.
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| CN 201110195338 CN102321277B (en) | 2011-07-12 | 2011-07-12 | Ionic crosslinked chitosan organic acid salt and Carboxymethyl chitosan or sulfated chitosan or sulfated carboxymethyl chitosan electrolyte composite film and preparation method thereof |
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| CN 201110195338 CN102321277B (en) | 2011-07-12 | 2011-07-12 | Ionic crosslinked chitosan organic acid salt and Carboxymethyl chitosan or sulfated chitosan or sulfated carboxymethyl chitosan electrolyte composite film and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103272264A (en) * | 2013-05-27 | 2013-09-04 | 杭州电子科技大学 | Sulfated polysaccharide calcium salt and chitosan organic acid calcium composite porous stent and preparation method thereof |
| CN110527147A (en) * | 2019-08-15 | 2019-12-03 | 华中农业大学 | A kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane |
| CN113248633A (en) * | 2021-06-25 | 2021-08-13 | 项斌 | Preparation method of low-molecular chitosan |
| CN116375892A (en) * | 2023-04-04 | 2023-07-04 | 徐州创力纤维有限公司 | Preparation method of polyanionic cellulose |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272264A (en) * | 2013-05-27 | 2013-09-04 | 杭州电子科技大学 | Sulfated polysaccharide calcium salt and chitosan organic acid calcium composite porous stent and preparation method thereof |
| CN110527147A (en) * | 2019-08-15 | 2019-12-03 | 华中农业大学 | A kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane |
| CN113248633A (en) * | 2021-06-25 | 2021-08-13 | 项斌 | Preparation method of low-molecular chitosan |
| CN113248633B (en) * | 2021-06-25 | 2022-06-21 | 时垠(上海)生物科技有限公司 | Preparation method of low-molecular chitosan |
| CN116375892A (en) * | 2023-04-04 | 2023-07-04 | 徐州创力纤维有限公司 | Preparation method of polyanionic cellulose |
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